Catalyst comprising molybdenum oxide, tellurium oxide and a manganese phosphate



United States Patent Ofilice 3,228,890 Patented Jan. 11, 1966 CATALYST COMPRISING MOLYBDENUM OXIDE, TELLURIUM OXIDE AND A MANGANESE PHOSPHATE Jamal S. Eden, Akron, Ohio, assignor to The B. F. Goodrich Company, New York, N.Y., a corporation of New York No Drawing. Filed Jan. 20, 1964, Ser. No. 338,617

10 Claims. (Cl. 252-437 This invention relates to a new and useful catalyst and to a method of preparing unsaturated aldehydes and unsaturated carboxylic acids by oxidation of unsaturated hydrocarbons at an elevated temperature and more particularly pertains to a catalyst comprising a mixture of a molybdenum oxide, tellurium oxide and a manganese phosphate in a molar ratio of 100 M -100 TeO and 10100 of a manganese phosphate and to a method of preparing acrolein, methacrolein, acrylic acid or methacrylic acid by passing vapors of propylene or isobutylene and an oxygen containing gas through the catalyst at a temperature of from about 325 C. to about 550 C. The catalyst can also be designated as with the P being in the form of a phosphate i.e. each P is attached to 3 or 4 oxygen atoms.

Numerous attempts have been made in the past to prepare products of higher oxidation state from hydrocarbons, especially from the normally gaseous hydrocarbons. However, all prior catalysts and procedures for oxidizing monoolefinic gaseous hydrocarbons to monoolefinically unsaturated aldehydes or monoolefinically unsaturated carboxylic acids with the same number of carbon atoms as the hydrocarbon having serious shortcomings. The catalysts either have a very short active life, or they convert only a portion of the hydrocarbon to desired end groups per pass; or they oxidize the hydrocarbon excessively to form proportions of carbon monoxide or carbon dioxide or both; or they are not sufiiciently selective, so that the hydrocarbon molecule is attacked at both the olefinic unsaturation and at a methyl group; or the oxidation of the olefin does not proceed beyond the aldehyde stage.

It is therefore unexpected to find a catalyst that will convert from about 70 to 100% of a gaseous monoolefin such as propylene or isobutylene per pass to yield very high proportions of acrolein, methacrolein and acrylic acid or methacrylic acid. It is also unexpected to find a catalyst that produces a Wide ratio of olefinic aldehyde to monoolefinically unsaturated carboxylic acid by controllable changes in reaction conditions or catalyst composition. It is possible to attain mol percent efficiencies of 1.4 to 53 for the aldehyde and 10.8 to 72.1 for the unsaturated carboxylic acid. Usually when the eificiency for conversion of the hydrocarbon to aldehyde is high the efficiency for the conversion to acid is low and vice versa. This provides a great degree of flexibility in the process, so as to provide means for obtaining a product mix that is needed at any particular time during operation.

A further unexpected feature is the unusually long active life of the catalyst.

The oxidation of propylene to the corresponding aldehyde and acid is more effective than the oxidation of isobutylene.

THE REACTANTS The only essential reactants are 1) propylene or isobutylene and (2) an oxygen containing gas, which can be pure oxygen, oxygen enriched air or air Without additional oxygen. For reasons of economy, air is the preferred oxygen containing reactant.

Stoichiometric ratios of oxygen to olefin for the purpose of this invention are 1.5 to 1. Slightly lower amounts of oxygen can be used at a sacrifice of yield.

It is preferred, however, to use 33 to 66% excess oxygen. Larger excess does not impair the yields of aldehydes and acids, but for practical considerations an excess much above would result in the requirement of extremely large equipment for a given production capacity.

The addition of steam into the reactor along with the hydrocarbon and oxygen containing gas is desirable but not absolutely essential. The function of steam is not clear, but it does seem to reduce the amount of carbon monoxide and dioxide in the effluent gases.

Other diluent gases can be used. Surprisingly, saturated hydrocarbons such as propane are rather inert under the reaction conditions. Nitrogen, argon, krypton or other know inert gases can be used as diluents if desired but are not preferred because of the added cost.

THE CATALYST AND ITS PREPARATION There are several methods for the preparation of the catalyst, which can be supported or unsupported.

It is possible to dissolve each of the starting ingredients in water and combine them from the aqueous solutions or the ingredients can be dry blended. Because of the more uniform blend obtained by the solution procedure, it is preferred.

The general procedure for preparing a catalyst from water soluble ingredients is to dissolve the requisite amount of a molybdenum salt, a tellurium salt and a manganese salt in Water. Add the requisite amount of phosphoric acid to the manganese salt solution. Add the tellurium salt solution to the molybdenum salt solution and then add the manganese salt-phosphoric acid mixture to the molybdenum-tellurium salt mixture. The catalyst is then dried and baked at 400 C. for about 16 hours.

Supported catalysts can be prepared by adding a dry support or an aqueous slurry thereof to the aqueous solution of catalyst or the aqueous catalyst ingredients can be added to the slurry of the support.

Alternately a slurry of the catalyst ingredients can be prepared in water, then dried and baked. For supported catalysts the aqueous slurry of the catalyst ingredients can be added to an aqueous suspension of the support or vice versa, and then dried and baked.

Another method is to blend the dry ingredients and then mix them thoroughly. The main difiiculty is to obtain thorough blending and uniform particle size.

Specific procedures for making catalysts are as follows:

(a) Dissolve 105.96 g. of (NH Mo O -4H O in 272 ml. Water at 50-55 C.

(b) Dissolve 53.76 g. NH4TCO4 in 900 ml. water at 50-55 C. and add to the molybdate solution with stirring.

3 The mixture may become cloudy, but no precipitate is formed.

(c) Dissolve 79.19 g. MnCl -4H O in 40 ml. water and add 46.2 g. of 85% H PO thereto.

Add the mixture described under (c) to the mixture of the ammonium molybdate and ammonium tellurate. No precipitate is formed but the final mixture remains cloudy.

If the catalyst is to remain unsupported, the mixture is evaporated to dryness on a steam bath, heated at 150- 200" C. for about an hour and then about 16 hours at 400 C. Then the catalyst is cooled, ground and sieved. For fixed bed systems a 10-18 mesh (U.S. Sieve) size is used. For fluid bed systems the catalyst should be 80-325 mesh (U.S. Sieve).

If the catalyst is to be supported the aqueous solution of ingredients can be added to an aqueous slurry of the support or vice versa, prior to drying. The procedure after drying is the same as that already described.

Thus, to the aqueous catalyst ingredients 240 g. (1.2 mols) of a colloidal silica (Ludox H.S.) are added slowly with stirring. Stirring is continued for about /2 hour prior to drying.

II.-*This procedure is a variant of Procedure I (a) Prepare a slurry of 43.189 g. M (99.5%

purity).

(b) Make a slurry of 15.961 g. TeO (Technical) in water and blend with (a) above.

(0) Dissolve 39.584 g. MnCl -4H O in water and add 23.1 g. 85% H PO Blend this mixture with the slurry of M00 and TeO Mix thoroughly and then dry and bake, or, if desired, add 120 g. Ludox H.S. to the catalyst before drying. Ludox H.S. is an aqueous colloidal dispersion of microspheroidal silica in a concentration of 30-35% SiO Another procedure is to add the mixture described under (c) to the Ludox and then add the requisite amount of TeO and M00 as a slurry.

Also, the ingredients can be added to the Ludox individually if desired.

III.In this procedure the ingredients are precipitated on nding (a) Dissolve 105.96 g. of ammonium molybdate in water at about 50 C.

(b) Dissolve 31.922 g. Te0 in concentrated HCl and filter if necessary.

Add the tellurium salt solution to the ammonium molybdate solution. A precipitate forms.

(c) Dissolve 79.168 g. MnCl-4H O in water and add 46.2 g. of 85 .H PO Add this mixture slowly to the precipitated ammonium molybdate-TeO mixture.

Dry on a steam bath and bake for 16 hours at 400 C. Thereafter, the catalyst is ground to the desired mesh size and sieved. For supported catalysts an aqueous slurry can be added to the catalyst ingredients, or vice versa, prior to drying and baking.

The fourth method is to grind M00 Te0 and a manganese phosphate to the proper particle size and then thoroughly mix the dry powders. The mixture can be added to an aqueous slurry of a support or vice versa and thereafter dried and baked.

The exact chemical structure of the catalysts made by the above procedures is not shown, but catalysts with molar ratios of 100 Mo, -100 Te and 10-100 of a manganese phosphate can be used for oxidizing the monoolefinic hydrocarbon to aldehyde and/or carboxylic acid. The catalyst contains chemically bound oxygen so that the generic formula can be written as M00 TeO 10 1o0 Mn P O or other Mn phosphate The phosphate can be a P0 radical, apyrophosphate or a polyphosphate.

Among the suitable supports are silica, silica containing materials, such as diatomaceous earth, kieselguhr, silicon carbide, clay, aluminum oxides and even carbon, although the latter tends to be consumed during the reaction.

The preferred catalyst is one having a ratio of M00 33.25 TeO and 33.25 Mn P O because it gives the highest yields of desired products and the preferred support is silica, because of its low cost and good fluidizing characteristics.

REACTION CONDITIONS The reaction can be carried out in either a fixed or fluidized catalyst bed.

The reaction temperature can range from about 300 to 450 C. for the oxidation of propylene but the preferred range is from about 350 to about 425 C. Below 350 C. the conversion per pass is lower than desirable and low temperature tends to produce more aldehyde than desired. Usually, a longer contact time is needed at lower temperatures to obtain the yields of desired products obtainable at higher temperatures.

Above 425 C. in the propylene oxidation some of the desired end products appear to be oxidized to carbon oxides. This is much more apparent at 450 C. For the isobutylene oxidation temperatures of 375-550 are desirable with the preferred range being 475-525 C.

The molar ratio of oxygen to propylene or isobutylene should be at least 2 to 1 for good conversion and yields, but ratios with some excess oxygen, 33 to 66 mol percent is even more desirable and is preferred. There is no critical upper limit as to the amount of oxygen, but when air is used as the oxygen containing gas it becomes apparent that too great an excess will require large reactors, pumping, compressing and other auxiliary equipment for any given amount of desired end product. It is therefore best to limit the amount of air to provide a 33 to 66% excess of oxygen. This range provides the largest proportion of acid, under given reaction conditions. Also, since care is needed to avoid an explosive mixture the limiting of air aids in that direction.

The molar ratio of steam to propylene or isobutylene can range from 0 to about 5, but best results are obtained with molar ratios of about 3.2 to 4.25 per mol of olefin and for this reason are preferred.

The contact time can very considerably in the range of about 2 to 70 seconds. Best results are obtained in a range of about 8 to 54 seconds and this range is preferred. Longer contact times usually favor the production of acid at any given temperature.

The particle size of catalyst for fixed bed and fluid bed systems has already been described.

The reaction can be run at atmospheric pressure, in a partial vacuum or under induced pressure up to 50-100 p.s.i. Atmospheric pressure is preferred for fixed bed systems and a pressure of 1 to 100 p.s.i. for fluid bed reactions. Care is needed to operate at a pressure which is below the dew point pressure of the unsaturated acid at the reaction temperature.

The data in the examples show that wide variations in percentages of unsaturated acids and aldehydes can be obtained with a single catalyst, using fixed ratio of reactants but changing the temperature and/ or contact time. Further variation is obtainable by controlling the other variables in the reaction including the catalyst compositions.

The examples are intended to illustrate the invention but not to limit it.

Example I A series of runs was made in a fixed bed reactor of a high silica (Vycor) glass tube 12 inches long and 30 mm. outer diameter. The reactor had three inlets, one for air, one for steam and one for propylene. Three external electrically operated heating coils were wound on the reactor. One of the coils extended along the entire length and the P is present as P 0 The catalyst was not supported and had a mesh size of 10-18 (U.S. Sieve).

Steam at a temperature of ZOO-250 C. was first passed into the reactor. Then propylene and air were separately fed into the stream of water vapor. This mixture then passed through a pre-heater and entered the reactor at about 200-250 C. The reactor was pro-heated to about 285 C. before the gas feed was begun.

The ratio of reactants was about 2.955 mols of oxygen and 4.16 mols of steam per mol of propylene. Cold contact time was 54 seconds.

The reaction temperature was varied as the reaction proceeded.

The table below summarizes the data obtained in these Aer. =Acr0lein. AA=Acrylic acid.

Repetition of run showed a yield of 3.3% acrolein and 70.8% acrylic acid.

In this set of experiments the only variable was the reaction temperature. It is apparent that if acrylic acid is the desired end product the reaction should preferably be held at about 405 to 415 C. If acrolein is the desired product lower temperatures of 350 C. or slightly below are preferred. Run No. 2 shows a combined efficiency of 84.5% with a ratio of acrolein to acrylic acid of about 1 to 1.2. Run No. 5 shows unusually good efficiency for acrylic acid production. It acrylic acid is the end product desired with a minimum of acrolein the conditions of this reaction can be followed.

Example 11 The catalyst and feed ratios were the same as those described under Example I. The cold contact time was 27 seconds. The reactor was similar to that described in Example I, but it had a length of 6 inches instead of 12. The amount of catalyst used was 85 ml.

A run at 400 C. showed 81.2% conversion of propylene with a mol percent yield, based on propylene converted, of 63 for acrolein and 27.5 for acrylic acid. The respective mol percent efficiencies are 51.1 and 22.4.

Another test made at 422 C. converted 95.4% of the propylene with a mol percent yield of acrolein of 46.3 and acrylic acid of 43.0. The respective mol percent efficiencies are 44.1 and 41.1.

This example shows that by reducing catalyst volume to one half that in Example I and also reducing the contact time 50% excellent efiiciencies are obtainable.

6 Example 111 The reactor, catalyst and catalyst volume were identical to those disclosed in Example I. The molar ratio of oxygen (supplied as air) to propylene in all runs was 3 to 1,

and the steam-propylene ratio was 4.25 to 1, on a molar basis. Cold contact time in each case was 41 seconds.

The data obtained are recorded below:

Mol percent M01 percent Mol percent yield on propylelficlency Run. No. Temp, propylene ene converted C. converted Aer. AA Aer. AA

Run No. 2 shows a combined efiiciency of 87.6, which is unusually high in view of the fact that there are numerous competing reactions going on concurrently, including the oxidation of the hydrocarbon to carbon monoxide and carbon dioxide.

Example IV In order to show the efiect of water vapor, a series of tests was made using a feed containing 3 mols of oxygen (supplied as air) per mol of propylene. The reactor, catalyst and catalyst volume were the same as described in Example I.

The data obtained in these runs are shown in the table below:

M01 percent M01 percent yield on propyl- Mol 1150/ Contact Temp., propylene ene converted propylene tune sec. C. converted Aer. AA

The mol percent efliciencies for each end product are the same as the yields, because conversion of the propylene was complete in all instances.

The data show that the presence of moisture is desirable but not essential to good yields of end products desired.

Example V The reactor, catalyst and catalyst volume were the same as described in Example I. The main variable was the difference in the amount of oxygen in the feed III, detailed above. The amount of catalyst employed was ml. in the 12 inch reactor. In each run the oxygen (fed as air) to propylene ratio was 3 to 1 and 4.25 mols of steam were fed per mol of propylene. The cold contact time was 41 seconds.

M01 percent; Yield on Propylene Converted Mol percent Percent Efliciency Temp. C.

Propylene M01 ratio of Catalyst per 100 mols Mo Converted TeO The above data show that a range of from 1080- mols TeO and 10-80 mols of a manganese phosphate per 100 mols of molybdenum compound can be employed to obtain good yields of acrolein and acrylic acid from the oxidation of propylene.

Example VII The runs of this example were made with an unsupported catalyst prepared by dissolving ammonium molybdate and ammonium tellurate in water and blending the two solutions and thereafter adding an aqueous solution Example VIII A catalyst was prepared by moistening 129.6 g. of M (99.5%), adding 47.88 g. TeO 42.56 g. MnO and 69.2 g. of 85% H PO in the order named. The mixture was thoroughly blended, dried and heated for 16 hours at 400 C. The catalyst was then ground and screened. Particles with a mesh size of -18 (U.S. Sieve) were used. The reactor was 12 inches long. It was charged with 170 ml. of catalyst. The data obtained with this catalyst are summarized below:

M01 Percent M01 Percent Contact Mol Percent Yield on Pro- Efiicieney Oz/CaHo 1120/ Time Temp. Propylene pylene CaHo Sec. C. Converted Converted Acr. AA Aer. AA

of manganese chloride and phosphoric acid. The molar Example IX ratio of ingredients was 100 Mo, 33.25 Te and 33.25 Mn P O For these tests 3 mols of oxygen (supplied as air) per mol of propylene and 4.25 mols of water per mol of propylene were fed into'a 12 inch reactor containing 170 ml. of the catalyst. Contact time was 41 seconds in all runs. Data recorded in these tests are tabulated below:

This example shows results obtained in a fixed bed system with a silica support catalyst. Catalyst A was prepared by adding the requisite amount of M00 (99.5% pure) in aqueous slurry to a colloidal silica (Ludox H.S.) with stirring, then a slurry of TeO was added with stirring and finally a solution of MnCl in H PO was added. The mixture was stirred, dried, and baked at 400 C. Catalyst B was prepared by making a solution of ammonium molybdate and ammonium tellurate in water and adding this to a colloidal silica which had some added ammonium hydroxide to prevent precipitation of the catalyst ingredients. Then an aqueous solution of MnCl and H PO was added. The mixture was stirred well, dried and baked at 400 C. for 16 hours. The reactor used was 6 inches long. It was filled with 85 ml. of catalyst. The molar ratio of ingredients in each catalyst was M0 33.25 TeO 33.25 Mn P O and 200 SiO 'uisite amounts of steam and propylene.

Data obtained are tabulated below:

10 The reactor was heated externally with electrical resistance wire, and the reaction temperature was controlled Catalyst A Mol Percent Yield on Mol Percent Contact Temp., M01 Percent Propylene Efliciency Time C Propylene Converted Og/CgH H O/ Sec. Converted CgHu Aer. AA Act AA 2. 5 3. 9 19 350 98. 3 47. 8 37. 2 47. 36. 6 2. 6 4. 1 24 345 98. 8 41. 0 41. 3 40. 5 40. 8 3. 0 3. 9 16 350 94. 8 50. 1 33. 0 47. 5 31. 3 3. 0 4. 1 21 350 98. 9 43. 4 37. 6 42. 9 37. 1 3. 0 4. 1 27 345 100 32. 5 43. 3 3. 0 3. 3 17 370 95. 8 55. 4 32. 0 53. 0 30. 6 3. 0 3. 3 21 372 99. 2 43. 6 38. 7 42. 2 38. 4 3. 0 4. 2 27 364 98.3 41.6 42.7 40.9 41.9 Catalyst B All the above examples illustrate the use of the new catalysts in fixed bed systems. amples in fluid bed systems. In each instance the catalyst was supported on diatomaceous earth. This support provided superior fiuidizing characteristics and provided better yields of desired products than the colloidal silica supported catalysts.

The supported catalyst employed in the fluidized bed was made as follows:

211.92 g. of ammonium molybdate were dissolved in 220 ml. H O at C. and 132 g. of diatomaceous earth (Celite V) were added and stirred until thorough blending was obtained.

102.2 g. of TeO were dissolved in 216 ml. of warm concentrated HCl and 105 g. of Celite V were added thereto.

To a solution of 158.3 g. of MnCl in 140 ml. of water were added 92.4 g. of H PO (aqueous) and 105 g. of Celite V were added to the mixture.

The tellurium oxide-HCl mixture was added to the mixture containing the manganese salt and blended thoroughly and the ammonium molybdate-Celite mixture 'was added last. The mixture was dried and baked at 400 C.

Celite V is a diatomaceous earth in granular form, with minor cristobalite structure. It has a bulk density of .39 g./cc., a skeletal density of 2.2 g./cc. determined in water, a surface area of 3-6 sq. meters/ g. and an average water absorption capacity of g./ g. of Celite.

The unsupported catalyst was made by Procedure III described above.

In these runs the reactor was a high silica glass cylin 'der with an 0.d. of 38 mm. and height of 5 ft. It was filled to a height of 10.5 inches for the unsupported catalyst and to a height of 24 inches for the supported catalyst. In all cases the catalyst was fluidized by first injecting hot air into the reactor and then adding the req- The gases were preheated to about 250 C. prior to entering the reactor.

The following are ex- 2 by use of rheostats to regulate the flow of current through the electrical heating wires.

The data obtained in the runs are given below:

M01 Percent Yield on Oz/CzHu H2O] Contact Temp., M01 Percent Propylene @211 Time, 0. Conversion Converted Sec. Propylene Aer. AA

UNSUPPORTED CATALYST SUPPORTED CATALYST Each of these catalysts was run for well over 100 hours without any apparent decrease in activity, even though reaction conditions in various runs were altered considerably.

The remaining examples were run in a fixed bed system.

Example X In this example two different catalysts were used, A had a molar ratio of 100 M00 33.25 TeO and 33.25 of Mn (PO and B had a molar ratio of 100 M00 33.25 Teo and 13.3 Mn w o h.

Mol Percent M01 Percent Contact Mol Percent Yield on Pro- Efiicicncy OglCaHg H2O] Time Temp. Propylene pylene C({Hfl Sec. C. Converted Converted Acr. AA Aer. AA

CATALYST A CATALYST B ll Example XI 2. A composition having the empirical formula 100 33.25 66.5 6B.5 599.25

in which P is present as a phosphate.

3. The composition of claim 1 impregnated on a silicic support. v

4. A composition having the empirical formula 100 2540 5080 5080 255660 in which the ratio of Mn to P is 1 to 1 and in which the P is present as a phosphate.

5. The composition of claim 3 in which the support is diatomaceous earth.

M01 Percent Yield Mol Percent O2/C4H HzO/C4Hg Contact Temp., Percent Isoon Isobutylene Eflieiency Time Sec. G. butylene Converted Converted Aldehyde Aeid Aldehyde Acid 170 ML. CATALYST VOLUME .85 ML. CATALYST VOLUME The catalyst had a molar ratio of 100 M00 25 TeO and 25 MIlzPzOq.

Example XII An unsupported catalyst made 'by Procedure III, using molar ratios of ingredients such that the M00 TeO and MHgPgOq was 1:1:1, was placed in the 12 inch fixed bed reactor hereinbefore described. The reaction mixture consisted of 1 mol of propylene, about 3 mols of oxygen, supplied as air, and 4.2 mols of water Vapor. The reaction temperature was 390 C. and the cold contact time was 54 seconds. All of the propylene was consumed, with a yield of 3.0% acrolein and 61.5% of acrylic acid.

For the purpose of this invention the hydrocarbons which are oxidized can be defined generically by the formula wherein it is also apparent that the end products formed result from the oxidation of only one methyl group on the hydrocarbon molecule while the terminal CH =C remains intact.

It is apparent to those skilled in the art that there are many variations in respect of catalyst, catalyst concentration, and reactant ratios that can be employed and that the invention shall not be limited except by the claims.

The method of impregnating a silicic carrier with individual ingredients of the catalyst system and thereafter combining the so impregnated carriers to complete the catalyst preparation is disclosed and claimed in patent application No. 380,683, filed July 6, 1964, in, the name of T. L. Kang.

I claim:

1. A composition consisting essentially of lo 1 10 2-2o 2-2o s9-12o in which the ratio of Mn to P ranges between Mu /P and Mn /P and in which each P is combined with from 3 to 4 atoms of oxygen.

6. A method of preparing a composition having catalytic activity for oxidizing C -C monoolefinic hydro.- carbons having a terminal CH C group to the corresponding monoolefinic aldehyde and carboxylic acid having the same number of carbon atoms as the hydro carbon, comprising preparing separate aqueous solutions of an inorganic molybdenum compound, an inorganic tellurium compound and an inorganic magnesium compound adding the aqueous solution of the tellurium compound to the solution of the molybdenum compound adding phosphoric acid to the solution of the manganese compound and adding the manganese compound-phosphoric acid mixture to the mixture containing the molybdenum tellurium compound, drying the resulting product and baking at an elevated temperature, the ratio of ingredients being such as to provide a product with the empirical formula MOmTe1 M1Il 2 P2 2 0 20 which each P is combined with 3-4 oxygen atoms and the Mn to P ratio ranges from SMn to GP to 3Mn to 2P.

7. A method of preparing a catalyst composition comprising (a) dissolving ammonium molybdate in Water (b) dissolving TeO in aqueous HCl I (c) dissolving manganese chloride in water and adding thereto suflicient H PO to provide a ratio of from 5Mn to 6P to 3Mn to 2P ((1) adding the manganese chloride-phosphoric acid mixture to the mixture of ammonium molybdate- TeCl and thereafter drying and baking the final mixture at a temperature of about 400 C., the molar ratio in the finished product being 8. The method of claim 7 in which the mixture of ingredients defined therein is blended with a silicic support prior to drying and baking.

9. The method of claim 8 in which colloidal silica is the support.

10. The method of claim 8 in which the support is diatomaceous earth.

(References on following page) 13 14 References Cited by the Examiner 3,065,264 11/1962 Koch et a1. 260-533 UNITED STATES PATENTS 3,102,147 8/1963 JOhIlSOIl 260-604 Rust et a1. 260533 Romanovsky et a1. 252-437 Romanovsky et a1. 252437 Hadley ct a1. 260533 BENJAMIN HENKIN, Primary Examiner. 5 LEON ZITVER, Examiner.

I. R. PELLMAN, Assistant Examiner. 

1. A COMPOSITION CONSISTING ESSENTIALLY OF 